Growth of Crystalline Copper Silicide Nanowires in High Yield within a High Boiling Point Solvent System

Geaney, Hugh; Dickinson, Calum; O’Dwyer, Colm; Mullane, Emma; Singh, Ajay; Ryan, Kevin M.

doi:10.1021/cm302066n

Cited by 33 publications

(54 citation statements)

References 56 publications

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“…Besides the intense peaks of the parent Cu, the diffraction patterns also show minor peaks intrinsic to the low temperature equilibrium silicide phases (Cu 15 Si 4 and Cu 0.83 Si 0.17 ), which can be assigned to the Cu x Si y network/intermediate layer. [ 11,14 ]…”

Section: Morphology Structure and Compositionmentioning

confidence: 99%

“…[ 2,4,9,10 ] Copper (Cu) is 40 times more conductive than stainless steel (SS) with a stable potential window, and is widely accepted as a suitable CC for LIBs. However, its application for direct growth of Si NWs is hampered by the energetically favorable formation of large crystallite grains and/or nanowire based Cu‐Si compounds, [ 11,12 ] that are inactive for Li‐cycling. [ 13,14 ] The formation of micrometer‐sized crystallite grains limits the ability to directly grow robust and pure phase Si NWs on Cu substrates.…”

Section: Introductionmentioning

confidence: 99%

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A Copper Silicide Nanofoam Current Collector for Directly Grown Si Nanowire Networks and their Application as Lithium‐Ion Anodes

Aminu

Geaney

Imtiaz

et al. 2020

Adv Funct Materials

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Silicon nanowires (Si NWs) have been identified as an excellent candidate material for the replacement of graphite in anodes, allowing for a significant boost in the capacity of lithium‐ion batteries (LIBs). Herein, high‐density Si NWs are grown on a novel 3D interconnected network of binary‐phase Cu‐silicide nanofoam (3D CuxSiy NF) substrate. The nanofoam facilitates the uniform distribution of well‐segregated and small‐sized catalyst seeds, leading to high‐density/single‐phase Si NW growth with an areal‐loading in excess of 1.0 mg cm−2 and a stable areal capacity of ≈2.0 mAh cm−2 after 550 cycles. The use of the 3D CuxSiy NF as a substrate is further extended for Al, Bi, Cu, In, Mn, Ni, Sb, Sn, and Zn mediated Si NW growth, demonstrating the general applicability of the anode architecture.

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Section: Morphology Structure and Compositionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Copper Silicide Nanofoam Current Collector for Directly Grown Si Nanowire Networks and their Application as Lithium‐Ion Anodes

Aminu

Geaney

Imtiaz

et al. 2020

Adv Funct Materials

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“…NW growth has been shown by self-induced solid phase seeding from bulk metal substrates 12,42 and also via VLS mechanism from evaporated catalytic layers that convert to discrete seeds under thermal anneal. The method allows the formation of both Si and Ge NWs using VLS (Sn 20 and In seeds 26 ) and VSS catalytic approaches (using bulk Cu 12,42 ) and has also been shown to allow seed-free Ge NW growth 41 directly from glass/Pyrex flask walls. 41,43 The use of p-block metals (e.g In and Sn) is interesting as although these have low melting points and a very low solubility for Si and Ge in the liquid eutectic, they allow for a high density of NW formation suitable for Li-ion alloying anodes.…”

Section: Physical Chemistry Chemical Physics Accepted Manuscriptmentioning

confidence: 99%

Synthesis of silicon–germanium axial nanowire heterostructures in a solvent vapor growth system using indium and tin catalysts

Mullane

Geaney

Ryan

2015

Phys. Chem. Chem. Phys.

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Here we describe a relatively facile synthetic protocol for the formation of Si-Ge and Si-Ge-Si1-xGex axial nanowire heterostructures. The wires are grown directly on substrates with an evaporated catalytic layer placed in the vapour zone of a high boiling point solvent with the silicon and germanium precursors injected as liquids sequentially. We show that these heterostructures can be formed using either indium or tin as the catalyst seeds which form in situ during the thermal anneal. There is a direct correlation between growth time and segment length allowing good control over the wire composition. The formation of axial heterostructures of Si-Ge-Si1-xGex nanowires using a triple injection is further discussed with the alloyed Si1-xGex third component formed due to residual Ge precursor and its greater reactivity in comparison to silicon. It was found that the degree of tapering at each hetero-interface varied with both the catalyst type and composition of the NW. The report shows the versatility of the solvent vapour growth system for the formation of complex Si-Ge NW heterostructures.

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“…Traditionally in electronic circuitry, metallic silicides have been widely used for Schottky diodes, metal gates, and local interconnections in complementary metal oxide-semiconductor (CMOS) devices. [8][9][10][11] A variety of metal silicide nanowires have been achieved by either silicidation of silicon nanowires, [12][13][14] delivery of Si ux on metal lms, 7,10,11,15 reactions of metals with silicon substrates, 16,17 or co-pyrolysis of organometallic precursors of metals and silicon via chemical vapor deposition (CVD) and chemical vapor transport (CVT). [3][4][5][6][7] The major challenging issues for the controlled growth of silicide nanomaterials are their many possible phases from metal-rich to silicon-rich silicides and complex phase behaviors within a narrow composition range.…”

Section: Introductionmentioning

confidence: 99%

Solution-phase synthesis of single-crystal Cu3Si nanowire arrays on diverse substrates with dual functions as high-performance field emitters and efficient anti-reflective layers

Yuan

Wang

et al. 2013

Nanoscale

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There is strong and growing interest in applying metal silicide nanowires as building blocks for a new class of silicide-based applications, including spintronics, nano-scale interconnects, thermoelectronics, and anti-reflective coating materials. Solution-phase environments provide versatile materials chemistry as well as significantly lower production costs compared to gas-phase synthesis. However, solution-phase synthesis of silicide nanowires remains challenging due to the lack of fundamental understanding of silicidation reactions. In this study, single-crystalline Cu3Si nanowire arrays were synthesized in an organic solvent. Self-catalyzed, dense single-crystalline Cu3Si nanowire arrays were synthesized by thermal decomposition of monophenylsilane in the presence of copper films or copper substrates at 420 to 475 °C and 10.3 MPa in supercritical benzene. The solution-grown Cu3Si nanowire arrays serve dual functions as field emitters and anti-reflective layers, which are reported on copper silicide materials for the first time. Cu3Si nanowires exhibit superior field-emission properties, with a turn-on-voltage as low as 1.16 V μm(-1), an emission current density of 8 mA cm(-2) at 4.9 V μm(-1), and a field enhancement factor (β) of 1500. Cu3Si nanowire arrays appear black with optical absorption less than 5% between 400 and 800 nm with minimal reflectance, serving as highly efficient anti-reflective layers. Moreover, the Cu3Si nanowires could be grown on either rigid or flexible substrates (PI). This study shows that solution-phase silicide reactions are adaptable for high-quality silicide nanowire growth and demonstrates their promise towards fabrication of metal silicide-based devices.

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Growth of Crystalline Copper Silicide Nanowires in High Yield within a High Boiling Point Solvent System

Abstract: Type of publicationArticle (

Cited by 33 publications

References 56 publications

A Copper Silicide Nanofoam Current Collector for Directly Grown Si Nanowire Networks and their Application as Lithium‐Ion Anodes

A Copper Silicide Nanofoam Current Collector for Directly Grown Si Nanowire Networks and their Application as Lithium‐Ion Anodes

Synthesis of silicon–germanium axial nanowire heterostructures in a solvent vapor growth system using indium and tin catalysts

Solution-phase synthesis of single-crystal Cu3Si nanowire arrays on diverse substrates with dual functions as high-performance field emitters and efficient anti-reflective layers

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